Protective composition for fruits and the like



Patented Sept. 6, 1938 Wendell H. 'lisdale, Cleveland Heights, Ohio,

and Albert L. Flenner, Wilmington, Dei., assignors, by mesne assignments, to E. I. 'du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application June 27, 1935,

Serial No. 28,700

10 Claims.

This invention relates to self-emulsifying compositions of matter useful as coating compositions in emulsified form and particularly for coating fruits, nuts; nursery stock, and the like for rosin in a' miscible form i high percentages in accordance with our formula which comprises essentially a mixture of rosin, wetting or dispersing agent, alcohol, and water in about the propertions of '15 to 40 parts of rosin, to 35parts of alcoholic hydrocarbon radical oi more than seven 5 reducing desiccation and decay, and for im-" wettingagent, 20 to 50 parts of alcohol, and 5 to 5 proving the condition and appearance of the 20 parts of water. A composition prepared in products. accordance with this formula forms a clear solu- Coating agents for application to fruits, nuts, tion which emulsifl'es with water upon mere adand other products, for retarding desiccation mixture therewith.

i0 and decay, and for improving the appearance and The rosin in our formula may be replaced in it condition of the products' are coming into coniwhole or in part by rosin esters of'glycerol or dimon use. Parail'ln and other waxes, such as ethylene glycol. K carnauba wax, are being used for this purpose. The wetting agent employed in our formulae Rosin, gelatin, and various other products have must be a member of thegroup consisting of albeen employed. The most eflicient means of apkyl-naphthalene-alkali-sulfonates. and sulfaplying waxes in the past has been in molten form tion products of aliphatic compounds which conwhich is expensive and likely to cause injury to tain an alcoholic hydrocarbon radical of more vfruit and the like if the temperature is not than seven carbon atoms. Other types of wetting properly controlled. More recently, emulsions of agents cannot be employed in our formulae if a 4 waxes have been prepared which can be applied composition is to be obtained which will readily as sprays or dips. These emulsions tend to break emulsify with water to form a stable emulsion in natural and hard waters and in the presence the presence of hard water and acid.

of weak acids such as those present in fruits. The sultation products of aliphatic com- For example, when citrus fruits are dipped in a pounds which contain-more than seven carbon 5 bath containing the ordinary waxemulsions, the atoms are obtained by reacting concentrated sulacids exude from broken fruit, dissolve in the furic acid, oleum, chlorosulfonic acid, or other bath, and soon break the emulsions causing them sulfuric acid derivatives of strongly sulfonatto separate and become unfit for further use. ing properties, upon aliphatic compounds which 80 An object of the present invention is to procontain an alcoholic hydrocarbon radical of more vlde compositions of matter which readily emulthan seven carbon atoms. According to the best sify, when mixed with water, to produce a stable experimental evidence available, the suliation coating composition for coating fruits, nuts, products of the alcohols are sulfuric acid esters nursery stock, and the like. A further object is of the probable formula ROS0aI-I with the to proyide emulsions useful as coating composipossible inclusion of minor amounts of sulfo'nic 35 tions which are stable in natural, hard waters and acids. When esters oi unsaturated alcohols are weak acids. A still further object is to provide sulfated,.= the sulfuric acid adds itself to the such compositionswhich maybe modified to prodouble bond, but the evidence available is in-' duce either a sticky coating or a smooth nonsuilicient todecide whether the products are sul- 40 tacky coating,-as desired. Another object is to furlc acid esters, sulionic acids, ora mixture 40 provide compositions which can be employed in of such compounds.

conjunction with'funglcidessuch as borax, and. As far as applicability to the purposes of our which will be stable in the presence of such mainvention is concerned, the reaction products obterials. Other objects areto provide methods of tained by the action of sulfuric acid, etc., upon preparing such coating compositions. Still other the alcohols or upon the unsaturated esters-are 45 4 objects are to provide new compositions of matter entirely equivalent, and for the purposes of our 3 and to advance the art. Further objects will invention we choose to call these products the appear hereinafter. sulfates of aliphatic compounds having an al- These objects may be accomplished in accordcoholic radical of more than seven carbon atoms. ance with our invention which comprises placing We believe that it is the presence oi an aliphatic so carbon atoms and of a salt forming sulfuroxygen group in the molecule that determines the v applicability of these compounds to our purposes.

As examples of aliphatic compounds from which the sulfates useful in our invention are derived, we may mention hexyl, octyl, decyl, pleyl, stearyl, cetyl, lauryl, carnaubyl, melissyl, myristyl, linoleyl, and ricinoleyl alcohols.

As additional examples of aliphatic compounds,

the sulfation products of which serve as wetting agents according to our invention, wemay mention aliphatic esters and ethers which contain an alcoholic radical of at least eight carbon atoms. We may use, for instance, acetyl-oleyl-alcohol, stearo-glyceryl-ether, oleo-glyceryl ether, and palmetto-glyceryl ether. As still further exam-- ples of starting materials,- we may mention aliphatic compounds which contain a chloro or other halogen group. In this connection it should be noted that when oleyl alcohol, for instance, is sulfated with chlorosulfonic acid, the treatment probably results in the introduction of a chlorogroup into some of the hydrocarbon radicals.

It is noted that ordinarily the starting material to be sulfated is a mixture of aliphatic compounds. This follows from the fact that the alcohols, esters,' and ethers of the types mentioned are produced commercially as mixtures and not as pure compounds, and it would be a costly and useless procedure to separate a particular alcohol, for instance, from others equally suitable.

The sulfates of aliphatic compounds such as those above mentioned form salts with such compounds as sodium carbonate, sodium hydroxide,

' potassium hydroxide, ammonium hydroxide, oxides and hydroxides of lithium, magnesium, etc.,

and with such amines as pyridine, piperidine, cyclo-hexylamine, monoand dialkyl cyclohexyl- 40 amines, dicyclohexylamines, mono-, di-, and trialkylamines, and mono-, di-, and trialkylolamines.

It is in the form of such salts that we usually add the sulfates to our novel composition. It is noted, though obvious, that the expression sulfation products of an aliphatic-compound which contains an alcoholic hydrocarbon radical of more than seven carbon atoms is generic to salts of the type above discussed. The commercialsalts frequently contain rather large amounts of impurities such as sodium sulfate, sodium chloride, etc., but these impurities do not interfere with the usefulness of the sulfates for the purposesof 3 our invention.

The alcohol employed alcohol, ethyl alcohol or propyl alcohol. Other alcohols such as isopropyl alcohol, butyl alcohol,

and the like cannot be employed to produce compositions having the desired properties of our compositions.

The compositions produced according to the above formula are clear solutions which maybe diluted with large volumes of water to produce stable emulsions or dispersions which will not break in hard waters or in the presenceof acids such as are present in citrus fruits.- when emulsions or dispersions produced from our compositions are applied to fruits, nuts, nursery stock, or foliage of trees and plants, they form coatings which adhere to the surfaces in the form of a sticky him. They are particularly adapted for addition to fungicidal and insecticidal spray materials and, when so used, hold the fungicide or Insecticide to the surfaces sprayed therewith.

when such a sticky coating is desired, it is generally preferred to replace part of the alcohol must be either methyl preferred embodiments thereof, the

aiaaovs with a paraffin oil of 65 to 120 seconds Saybolt at 100 1?. Up to three-fifths of the alcohol may be replaced with such oil. However, the alcohol and oil combination must amount to 20 to parts and at least two-fifths of the combination must consist of alcohol.

and causes it to retain such properties over a longer period of time. I

' It is frequently desirable to reduce the tackineas of the coating and to produce a smooth non-tacky coating on fruits, nuts, nursery stock. and the. like to improve the appearance thereof and to protect them from desiccation and decay. In such case, there may be added to the formula. up to 20 parts of a higher aliphatic alcohol which is immiscible with water and solid at ordinary temperatures. Such alcohols contain at least 15 carbon atoms and, preferably, are primary monohydric alcohols. Representative alcohols are stearyl, cetyl, ceryl, myricyl, and octadecyl alcohols. Of these, crude or technical stearyl alcohol, generally known to the trade as stenol and containing minor amounts of other alcohols mostly cetyl alcohol, has given the best results. These alcohols may be present up to 20 parts and may be-present in amounts equal to that of the rosin. Also, the amount of the rosin and higher alcohol together must not amount to more than about 40 parts. When these higher alcohols are employed, the paraffin oil is generally not employed and will generally be found to. be undesirable.

Our compositions containing the higher alcohols are clear solutions which are stable on standing and which can be diluted with large volumes of water to form stable emulsions or dispersions which do not break in the presence of hard water or acids such as are found in citrus fruits. When they are applied to fruit and the like in the proper dilutions, they form smooth coatings of reduced tackiness. In fact, when the relative proportion of rosin and higher alcohol mounts to approximately equal parts of rosin and alcohol, the coating is non-tacky.

We have found that the ingredients and the relative proportions as given above are impor-.

taut. If other wetting agents or other lower molecular weight alcohols are substituted for those' "specified, a clear homogeneous solution which will readily emulsify with water and-particularly with hard and acidic water will not be The paraflln oil, when employed, increases the stickiness of the coating produced. When such other wetting agents or alcohols are employed, it will be impossible to obtain a homogeneous mixture, or the mixture will separate on standing. Also, if such other wetting agents or alcohols are employed, some of the ingredients will separate out on diluting with water, particularly if the water is hard or contains acids. Furthermore, if the ingredients or the relativ proportions thereof are varied to any material extent outside of the ranges given above, a clear stable solution readily emulsiflable with water will not be produced. For example, the rosin,

, wetting agent, and alcohol cannot be added to a large volume of water to obtain the desired emulsion. On the other hand, if the ingredients are mixed in accordance with our formula, the resulting clear solution may then be added to a large volume of water and readily mixed therewith to form a stable emulsion.

In order to illustrate our invention and the following examples are given.

[I Example I A preferred composition was prepared according to the following in which the parts are by weight:

Parts Rosin 20 Crude stearyl alcohol.. 20 Technical octyl sodium sulfate 10.5 Ethyl nlnnhnl 30 Water 19.5

The composition was warmed to about the melting point of the rosin to aid in mixing. A similar procedure was followed also in the succeeding examples. The composition of this example was a clear solution which readily emulsified with water. The emulsion was particularly desirable for producing a smooth, non-tacky coating on fruits, nuts, nursery stock, and the like. The emulsion was very stable, and, as will be pointed out hereinafter, borax and the like can be used with it without causing the emulsion to break.

Example II A composition was prepared from the following ingredients mixed in the indicated proportions in which the parts are by weight.

, Parts Crude stearyl alcohol 15 Ethyl alcohol 47 Sulfation product of oleyl acetate 12 Sodium salt of a sulfation product of a commercial mixture of even numbered straight chain alcohols from C12 to-Cm 6 Water This composition was a clear solution which readily emulsified with water upon mixing therewith. The emulsion was found to be particularly desirable for producing a smooth coating on fruits; nuts, nursery stock, and the like. The coating so produced was non-tacky and capable of preventing desiccation and decay of the coated materials over extended periods of time and of materially improving the apearance thereof.

Erample III A composition was prepared as follows;

Parts Rosin 20 Rosinflqpter of diethyleneglycol 20 Parafiln iigi Sulfation iiroduct of oleyl acetate 24.5 Ethyl alcohol 10' Water a 10.5

f The resulting mix was a clear solution, readily forming a stable emulsionwhen mixed with alarge amount of water. The resulting emulsion, when sprayed on fruit, nuts, nursery stock, and the foliage of trees and plants, adhered to the surfaces thereof tenaciouslyto form a sticky coating. This composition is particularly desirable for use as a spreading and sticking agent to be added to insecticidal and fungicidal spray materials. Example W l A composition consisting of the following ingredients was prepared:

Parts Rosin Rosin ester of diethylene glycol 20 Paraffin oil 15 Isopropyl naphthalene sodium sulfonate 17.5 Ethyl alcohol 10 Water 12 This was a clear solution readily emulsifiable with water to produce a stable emulsion. The resulting emulsion produced a tacky coating on the materials treated therewith. This composition is particularly useful as a spreading and sticking agent to be added to insecticidal and fungicidal spray materials Example V A composition was prepared in accordance with the following formula:

Parts Rosi 30 Technical stearyl alcohol l0 Sulfation products of oleyl acetate 14 Sulfate ester of oleyl alcohol 8 Ethyl alcohol 30 Water 8 Upon mixing, these ingredients formed a clear solution readily emulsifiable with water. The

resulting'emulsion was useful as a coating agent to produce a smooth non-tacky coating on fruits, nuts, nursery stock, and the like when diluted in proper proportions.

Example VI A composition was prepared in accordance with the following formula:

Parts Rosin 30 Crude stearyl alcohol l0 'Sulfation product of oleyl acetate 24.5 Ethyl alrnhn] Water.-- 10.5

Examp e VII To the composition given in any of the foregoing examples may be added up to 5% or more of tetra ethyl thiuram monosulflde which is soluble in the mixture and which has been found to be an excellent fungicide when used in the proportions of about 2 to 5%.

Other fungicides soluble in the mixture may also be used, but only those safe on foodprod-- ucts should be employed in fruit coating compositions.

Borax is commonly used W for'treating citrus fruit to prevent fungous decay in storage and transit. Because of the ability of these emulsions to withstand hard waters, borax may be dissolved in the water or in the emulsion in suflicient strength to serve as a disinfectant at the timethe composition is diluted'for application. I p Example VIII v Compositions used for coating fruit, such as our preferred composition of Example 1, may be diluted in a 4% borax solution in preparing the emulsion for application. It is preferable to dissolve the borax in the water before mixing in the coating composition.

For the treating of nursery stock and other items not used for food, a wider range of fungicides is available, both for including in the composition and for dissolving in the water before adding the composition.

Example 1X To the coating compositions above disclosed may be added 0.5% to 1.0% of ethyl mercury oleate or phenyl mercury oleate which is sumcient for disinfecting purposes. More could be added if needed. Copper oleate, copper resinate, :nd otidier compounds of similar solubility could e use -Water soluble copper, mercury, and organic disinfectants can likewise be used in the water employed for diluting the compositions for ap-" plication to articles not used for food.

The compositions prepared in accordance with our invention form emulsions or dispersions which are stable in the presence of natural, hard waters and weak acids. Hence, they have all the advantages of the prior wax emulsions and the like and also many advantages thereover.

While we have disclosed the preferred embodiments of our invention, it will be apparent to those skilled in the art. that many variations and changes may be made therein without departing from the spirit thereof. Accordingly, the scope of this invention is to be limited solely by the appended claims construed as broadly as is permissible in view of the prior art.

We claim: I l

1. A self-emulsifying composition of matter useful as'a coating composition in emulsified form characterized in emulsified form by its stability in the presence of either weak acids or the impurities of hard or natural water or in the presence of both which comprises in admixture'about 15 to about 40 partsof at least one member of the group consisting of rosin, glycerol esters of rosin and diethylene glycol esters of rosin, about ,10 to about 35 parts of at least one wetting agent of the group consisting of sulfation products of aliphatc compounds which contain an alcoholic radical of more than 7 carbon atoms and alkylnaphthalene-alkali-sulfonates, about 20 to about 50 parts of a composition consisting of from about two-fifths to flvefifths of at least one primary monohydric alcohol of not more than three carbon atoms, the bal- 'ance being a paraffin oil, and about to about 20 parts of water, all parts being by weight. 2. A self-emulsifying composition of matter useful as a coating composition in emulsified form characterized in'emulsified' form by its stability in the presence of either weak acids or the impurities .of hard or natural water or in the presence of bothwhich comprises in admixture about 15 to about 40 parts of at least one member of the group consisting of rosin glycerol esters of rosin and rosin ester of diethyleneglycol, about 10 to about 35 parts of at least one wetting agent of the group consisting'of sulfation products of aliphatic compounds which contain an. alcoholic radical of more than 7 carbon atoms and isopropyl naphthalene sodium sulfonate, about 20 to about 50 parts of a composition consisting of from about two-fifths to five-fifths of at least one primary monohydric alcohol of not more than three carbon atoms, the balance being a paraflin oil, and about 5 to about 20 of water, all parts being by weight.

3. A self-emulsifying composition of matter useful as'a coating composition in emulsified form characterized in emulsified form by its stability in the presence of either weak acids or the impurities of hard or natural water or in the presence of both which comprises in admixture about to about 40 parts of at least one member of the group consisting of rosin. glycerol esters of rosin and di-ethylene glycol esters of rosin, up to about parts of at least one aliphatic alcohol containing at least 15 carbon atoms, the alcohol and rosin combined amounting to not more than about 40 parts and the rosin comprising at least half of the combination, about 10 to about 35 parts of at least one wetting agent of the group consisting of sulfation products of aliphatic compounds which contain an alcoholic radical of more than 7 carbon atoms, and alkyl-naphthalene-alkali-sulfonates, about 20 to about 50 parts of at least one primary monohydric aliphatic saturated alcohol of not more to about 40 parts of at least one member of the group consisting of rosin, glycerol esters of rosin and diethylene glycol esters of rosin, about 10 to about parts of at least one wetting agent of the group consisting of sulfation products of aliphatic compounds which contain an alcoholic radical of more than 7 carbon atoms and alkyinaphthalene-alkali sulfonates, about 5 to about 20 parts of water, paraflln oil and a monohydric alcohol of not more than three carbon at o said paraflinoil and alcohol amounting to about 20 to 50 parts of which at least about two-fifths is alcohol and in which the paramn oil is present in an amount sufficient toimpart stickiness, all parts beingby weight.

5. As 'a spreading and sticking agent for agricultural sprays, a self-emulsifying composition,

I characterized in emulsified form by stability in the presence of the impurities of hard or natural water, which comprises in admixture rosin, rosin ester of diethylene glycol, a sulfation product of oleyl acetate,paraflln oil, ethyl alcohol and water, the rosin and rosin ester of diethylene glycol amounting to about 15 to about 40 parts, the sulfation product of oleyl acetate to about 10 to about 35 parts, the paramn oil and ethyl alcohol to about 20 to about 50 parts 5 to 20 parts, all partsbeing by weight.

of which at least about two-fifths is ethyl alcohol and the water to about 6. The method of preparing a stable emulsion useful as-a coating composition which consists of mixing together about 15 to about do'parts of at least one member of the group consisting of rosin, glycerol esters of rosin and diethylene glycol esters of rosin. about 10 to about 35 parts of at least one wetting agent of the group consisting of sulfation products of aliphatic. compounds which contain an alcoholic radical of more than 7 carbon atoms and alkyl-naphthalenealkali-sulfonates, about 20 to about parts of a composition consisting of from about two-fifths to five-fifths of at least one primary monohydric alcohol of not more than three carbon atoms,

the balance being a paraflin oil, and about 5 to about 20 parts of water, and then diluting resulting mixture with a large volume of water,-

all parts being by weight; a

'7. The method of preparing a stable emulsion useful as a" coating composition which consists of mixing together about 15 to about 40 parts of at least one member of the group consisting 7s of rosin, glycerol esters of rosin and rosin ester of diethylene glycol, about to about 35 parts of at least one wetting agent of the group consisting of sulfation products of aliphatic compounds which contain an alcoholic radical of more than 7 carbon atoms and is propyl-naphthawater; all partsbeing by weight.

8. The method of preparing an emulsion characterized by stability in the presence of the impurities of hard or natural water, which comprises mixing together about to about 40 parts of at least one member of the group consisting of rosin, glycerol esters of rosin and diethylene glycol esters of rosin, about 10 to about parts I of at least one wetting agent of the group consisting of sulfation products of aliphatic compounds which contain an alcoholic radical of more than 7 carbon atoms and alkyl-naphthalene-alkali sulfonates, about 5 to about 20 parts of water, parafiln oil and a monohydric alcohol of not more than three carbon atoms, said paraflin oil and alcohol'amountingto about 20 to 50 parts of which at least about two-fifths is alcohol and in which the paraflin oil is present in an amount :sufilcient to impart stickiness,

and then diluting the resulting mixture with a large volume of water, all parts being by weight.

9. The method of preparing an emulsion characterized by stability in the presence of the impurities of hard or natural water, which comprises mixing together rosin, rosinester of diethylene glycoLasulfation product of oleyl acetate, paraffin oil, ethyl alcohol and water, the rosin and rosin ester of diethylene glycol amounting to about 15 to about 40 parts, the sulfation prodnot of oleyl acetate to about 10 to about 35 parts, the parafiin oil and ethyl alcohol to about 20 to about parts of which at least about twofifths is ethyl alcohol and the water toabout 5 to 20 parts, and then diluting the resulting mixture with a large volume of water, all parts being by weight.

10. As va spreading and sticking agent for agricultural sprays, a self-emulsifying composition characterized in emulsified form by its stability in the presence of either weak acids or the impurities of hard or'natural water or in the presence of both which comprises in admixture' about 20 parts of rosin, about 20 parts of a rosin ester of diethylene glycol, about 15 parts of paraifin oil, about 24.5 parts of a sulfation product of oleyl acetate, about 10 parts of ethyl alcohol, and about 10.5 parts of water,'all parts being by'weight.

WENDELL H. TISDALE. ALBERT L. FLENNER. 

